EP3988523A1 - Procédé de production de molécules organiques fonctionnalisées et leurs utilisations - Google Patents

Procédé de production de molécules organiques fonctionnalisées et leurs utilisations Download PDF

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Publication number
EP3988523A1
EP3988523A1 EP20382918.9A EP20382918A EP3988523A1 EP 3988523 A1 EP3988523 A1 EP 3988523A1 EP 20382918 A EP20382918 A EP 20382918A EP 3988523 A1 EP3988523 A1 EP 3988523A1
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EP
European Patent Office
Prior art keywords
bar
ethanol
process according
carried out
hydroxyapatite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP20382918.9A
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German (de)
English (en)
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EP3988523B1 (fr
Inventor
Pau TURÓN DOLS
Vanesa SANZ BELTRÁN
Anna Maria RODRÍGUEZ RIVERO
Carlos Enrique ALEMÁN LLANSÓ
Jordi PUIGGALÍ BELLALTA
Guillem REVILLA-LÒPEZ
Jordi Sans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universitat Politecnica de Catalunya UPC
B Braun Surgical SA
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Universitat Politecnica de Catalunya UPC
B Braun Surgical SA
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Priority to ES20382918T priority Critical patent/ES2942302T3/es
Application filed by Universitat Politecnica de Catalunya UPC, B Braun Surgical SA filed Critical Universitat Politecnica de Catalunya UPC
Priority to EP20382918.9A priority patent/EP3988523B1/fr
Priority to IL297651A priority patent/IL297651A/en
Priority to CA3180731A priority patent/CA3180731A1/fr
Priority to ES21720783T priority patent/ES2940284T3/es
Priority to BR112022021718A priority patent/BR112022021718A2/pt
Priority to CN202180046076.6A priority patent/CN115956000A/zh
Priority to PCT/EP2021/060996 priority patent/WO2021219644A1/fr
Priority to JP2022565842A priority patent/JP2023524232A/ja
Priority to EP21720783.6A priority patent/EP3953021B1/fr
Priority to KR1020227041561A priority patent/KR20230005915A/ko
Priority to AU2021266106A priority patent/AU2021266106A1/en
Priority to US17/921,755 priority patent/US20230159417A1/en
Publication of EP3988523A1 publication Critical patent/EP3988523A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/159—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with reducing agents other than hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis

Definitions

  • the present invention relates to a process for producing functionalized organic molecules, in particular having 1 to 3 carbon atoms, and to uses thereof.
  • Carbon dioxide (CO 2 ) is considered the primary greenhouse gas and the main cause for global climate warming. Therefore, the efficient utilization of it as C1 feedstock to synthesize valuable chemical and industrial products is drawing increasing attention.
  • carbon dioxide may be employed as C1 feedstock to synthesize ethanol ( W. Zhang, Y. Hu, L. Ma, G. Zhu, Y. Wang, X. Xue, R. Chen, S. Yang. Z. Jin, Adv. Sci. 2018, 5, 1700275 ; B. An, Z. Li, Y. Song, J. Z. Zhang, L. Z. Zeng, C. Wang, W. B. Lin, Natur. Catal. 2019, 2, 709-717 ; C. Liu, B. C. Colon, M.
  • transition metals and complexes that can act as transition metals dominate the catalysis associated to CO 2 activation and fixation ( C. S. Yeung, Angew. Chem. Int. Ed. 2019, 58, 5492-5502 ; C. Weetman, S. Inoue, ChemCatChem 2018, 10, 4213-4228 ; P. P. Power, Nature 2010 463 171-177 ; D. D. Zhu, J. L. Liu, S. Z. Adv. Mater. 2016, 28, 3423-3452 ).
  • the carbon atom in CO 2 is at the highest oxidation state, the CO 2 molecule is very inert and stable. Therefore, the conversion of CO 2 into high-value chemicals with one carbon atom (C1; as for example methanol and formic acid), two carbon atoms (C2; as for example ethanol and acetic acid) and three carbon atoms (C3; as for example acetone) requires very efficient electrocatalysts for promoting the kinetically sluggish CO 2 reduction process.
  • C1 carbon atom
  • C2 two carbon atoms
  • C3 as for example acetone
  • the object underlying the present invention is therefore to make available a process for producing, in particular selectively producing, functionalized organic molecules, in particular having 1 to 3 carbon atoms, which addresses the afore-mentioned need.
  • the present invention relates to a process for producing or synthesizing, in particular selectively producing or synthesizing, functionalized organic molecules, in particular having 1 to 3 carbon atoms, wherein the functionalized organic molecules are preferably selected from the group consisting of ethanol, methanol, formic acid, acetic acid, malonic acid, acetone and a mixture of at least two of the afore-said functionalized organic molecules.
  • the present invention relates to a process for producing or synthesizing, in particular selectively producing or synthesizing, ethanol or a mixture comprising or consisting of ethanol and at least one further functionalized organic molecule, preferably selected from the group consisting of methanol, formic acid, acetic acid, malonic acid and acetone, in particular to a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone, in particular with ethanol as a major reaction product, or to a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone, in particular with ethanol as a major reaction product.
  • the process comprises the step of
  • the term "functionalized organic molecules” as used according to the present invention means organic molecules bearing or comprising functional groups, i.e. specific substituents or moieties that are typically responsible for the characteristic chemical reactions of the organic molecules.
  • the functional groups are selected from the group consisting of carboxy groups, formyl groups, keto groups, hydroxy groups and combinations thereof.
  • the term "functionalized organic molecules" as used according to the present invention may refer to one type of organic molecule, for example an alcohol such as ethanol or a carboxylic acid such as formic acid, or to a mixture comprising or consisting of different organic molecules.
  • the different organic molecules for example, may be different in terms of the number of carbon atoms and/or the functional group.
  • the term "functionalized organic molecules" as used according to the present invention means carboxylic acids, aldehydes, ketones, alcohols or mixtures thereof. More preferably, the carboxylic acids/carboxylic acid are/is formic acid and/or acetic acid and/or malonic acid. The ketones/ketone are/is preferably acetone. The alcohols/alcohol are/is preferably ethanol and/or methanol.
  • the process according to the present invention is preferably a process for producing or synthesizing, in particular selectively producing or synthesizing, carboxylic acids, in particular different carboxylic acids, having 1 to 3 carbon atoms, preferably formic acid and/or acetic acid, and/or malonic acid, and/or aldehydes, in particular different aldehydes, having 1 to 3 carbon atoms and/or ketones, in particular different ketones, having 1 to 3 carbon atoms, preferably acetone, and/or alcohols, in particular different alcohols, having 1 to 3 carbon atoms, preferably ethanol and/or methanol.
  • the process according to the present invention is a process for producing or synthesizing, in particular selectively producing or synthesizing, functionalized organic molecules which are selected from the group consisting of ethanol, methanol, formic acid, acetic acid, malonic acid, acetone and mixtures thereof, i.e. mixtures of at least two of the afore-said functionalized organic molecules.
  • the process according to the present invention is a process for producing or synthesizing, in particular selectively producing or synthesizing, ethanol or a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone, in particular with ethanol as a major reaction product, or a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone, in particular with ethanol as a major reaction product.
  • major reaction product in particular in the context of ethanol, as used according to the present invention means a product having the highest molar yield within a mixture comprising or consisting of different products, in particular different functionalized organic molecules, in particular having 1 to 3 carbon atoms.
  • the term "permanently polarized hydroxyapatite” as used according to the present invention means a hydroxyapatite that has undergone a complete structural redistribution, in particular almost perfect, with a high crystallinity degree, i.e. particularly with a low amount of amorphous calcium phosphate and the presence of vacancies detected by increased electrochemical activity and the accumulation of charge per unit mass and surface. It has an electrochemical activity and ionic mobility which do not disappear over time.
  • the corresponding 31 P-NMR spectrum of the permanently polarized hydroxyapatite is as shown on fig. 1 .
  • said spectrum is carried out with solid hydroxyapatite using phosphoric acid (H 3 PO 4 ) as a reference and showing a unique peak at 2.6 ppm corresponding to phosphate groups of hydroxyapatite.
  • thermal polarized hydroxyapatite preferably means a permanently polarized hydroxyapatite obtained or obtainable by a process (thermal polarization process) comprising the steps of
  • the samples of hydroxyapatite in step (a) may be samples of a natural, i.e. naturally occurring, hydroxyapatite or of a synthetic hydroxyapatite.
  • samples of hydroxyapatite in step (a) may be in particular selected from the group consisting of samples of crystalline hydroxyapatite, samples of amorphous hydroxyapatite, samples of a mixture of crystalline hydroxyapatite and amorphous calcium phosphate, and mixtures thereof.
  • the permanently polarized hydroxyapatite of the composition or material according to the present invention is preferably obtained or obtainable by the above process (thermal polarization process).
  • room temperature means a temperature from 15 °C to 35 °C, in particular 18 °C to 30 °C, preferably 20 °C to 30 °C, more preferably 20 °C to 28 °C, particularly 20 °C to 25 °C.
  • the present invention rests on the surprising finding that production or synthesis, in particular selective production or synthesis, of functionalized organic molecules having 1 carbon atom (such as methanol and/or formic acid), functionalized organic molecules having 2 carbon atoms (such as ethanol and/or acetic acid) and functionalized organic molecules having 3 carbon atoms (such as acetone) from carbon dioxide alone or from carbon dioxide and methane in the presence of permanently polarized hydroxyapatite as catalyst is achievable under mild conditions (particularly ⁇ 10 bar pressure and ⁇ 250 °C, in particular ⁇ 250 °C, temperature) with lower levels of environmental contamination and cost.
  • functionalized organic molecules having 1 carbon atom such as methanol and/or formic acid
  • functionalized organic molecules having 2 carbon atoms such as ethanol and/or acetic acid
  • functionalized organic molecules having 3 carbon atoms such as acetone
  • the production or synthesis of functionalized organic molecules having 1 to 3 carbon atoms involves hydrogenation of reduced carbon dioxide and C-C bond construction.
  • the process according to the present invention may also be denoted as electro-reduction process of carbon dioxide towards carboxylic acids (such as formic acid and/or acetic acid) and/or aldehydes and/or ketones (such as acetone) and/or alcohols (such as methanol and/or ethanol) and the permanently polarized hydroxyapatite may also be denoted as electro-catalyst.
  • the permanently polarized hydroxyapatite comprises or has
  • bulk resistance means resistance to the electron transfer and may be determined by means of electrochemical impedance spectroscopy.
  • the bulk resistance increases by only 0.1 % to 33 %, in particular 4 % to 63 %, preferably by 4 %, after 3 months.
  • surface capacitance means capacitance attributed to surface changes of hydroxyapatite induced by a thermal polarization process and may be determined by means of electrochemical impedance spectroscopy.
  • the permanently polarized hydroxyapatite is obtained or obtainable by a process comprising the steps of
  • samples as used according to the present invention may in particular mean one sample, i.e. only one sample (singular), or a plurality of samples, i.e. two or more samples.
  • shaped bodies as used according to the present invention may in particular mean one shaped body, i.e. only one shaped body (singular), or a plurality of shaped bodies, i.e. two or more shaped bodies.
  • the aforementioned step (a) may be carried out by using ammonium phosphate dibasic (diammonium hydrogen phosphate, (NH 4 )2HPO 4 ) and calcium nitrate (Ca(NO 3 ) 2 ) as reactants or starting materials.
  • the step (a) may be carried out by
  • the step (a 1 ) may be in particular carried out by using a mixture comprising or consisting of ammonium phosphate dibasic, calcium nitrate, water, in particular de-ionized water, ethanol, and optionally chelated calcium solutions.
  • the pH value of the mixture and/or the pH value of an aqueous calcium nitrate solution applied for providing the mixture may be adjusted to 10-12, preferably 10.5.
  • shapes and sizes of hydroxyapatite, in particular in the form of nanoparticles can be controlled.
  • the step (a 2 ) may be carried out under agitation, in particular gentle agitation, for example applying 150 rpm to 400 rpm.
  • the step (a 2 ) may be carried out for 1 min to 12 h, in particular for 1 h.
  • the step (a 2 ) may also be termed as an aging step, according to the present invention.
  • the step (a 3 ) may be carried out at a temperature of 60 °C to 240 °C, preferably of 150 °C.
  • the step (a 3 ) may be carried out at a pressure of 1 bar to 250 bar, preferably of 20 bar.
  • the step (a 3 ) may be carried out for 0.1 h to 72 h, preferably for 24 h.
  • step (a 4 ) may be carried out by cooling the mixture hydrothermally treated in step (a 3 ) to a temperature of 0 °C to 90 °C, in particular of 25 °C.
  • step (a 5 ) may be carried out by means of centrifugation and/or filtration.
  • the precipitates separated in step (a 5 ) may be washed, in particular using water and/or a mixture of ethanol and water, before the step (a 6 ) is carried out.
  • the step (a 6 ) may be carried out for 1 day to 4 days, in particular for 2 days to 3 days, preferably for 3 days.
  • step (b) may be carried out at a temperature between 700 °C and 1150 °C, in particular between 800 °C and 1100 °C, in particular at 1000 °C.
  • the process preferably comprises between the step (b) and the step (c) a further step (bc)
  • the step (bc) may be carried out under a pressure of 1 MPa to 1000 MPa, in particular 100 MPa to 800 MPa, preferably 600 MPa to 700 MPa. Further, the step (bc) may be carried out for 1 min to 90 min, in particular 5 min to 50 min, preferably 10 min to 30 min.
  • the shaped bodies may have a polygonal, for example triangular, quadratic or rectangular, pentagonal, hexagonal, heptagonal, octagonal or nonagonal, or a corner-less, in particular circular, oval-shaped or elliptical, cross-section.
  • the shaped bodies may have a thickness of > 0 cm to 10 cm, in particular > 0 cm to 5 cm, preferably > 0 cm to 2 cm.
  • the shaped bodies may have a thickness of 0.1 cm to 10 cm in particular 0.1 cm to 5 cm, preferably 0.5 cm to 2 cm.
  • the shaped bodies are in the form of discs, plates, cones or cylinders.
  • step (c) catalytic activation of the samples obtained in step (b) or the shaped bodies thereof may be accomplished.
  • step (c) is carried out by placing the samples obtained in step (b) or by placing the shaped bodies thereof between a positive electrode and a negative electrode, wherein the samples obtained in step (b) or the shaped bodies thereof are in contact with both electrodes.
  • the electrodes may, by way of example, be in the form of stainless steel plates, in particular stainless steel AISI 304 plates. Further, the electrodes may have a mutual distance of 0.01 mm to 10 cm, in particular 0.01 mm to 5 cm, preferably 0.01 mm to 1 mm.
  • the electrodes can be of different shapes.
  • the electrodes may have a polygonal cross-section, for example quadratic or rectangular, or a corner-less, in particular circular, oval-shaped or elliptical, cross-section.
  • the shaped body may have a thickness of > 0 cm to 10 cm in particular > 0 cm to 5 cm, preferably > 0 cm to 1 mm.
  • the electrodes may be in the form of a disc, plate or a cylinder.
  • the constant or variable DC voltage or the equivalent electric field may be applied in the aforementioned step (c) for 1 h to 24 h, in particular 0.1 h to 10 h, in particular 1 h.
  • the DC voltage applied in the aforementioned step (c) is preferably 500 V, which is equivalent to a constant electric field of 3 kV/cm.
  • the equivalent electric field applied in the aforementioned step (c) is preferably 3 kV/cm.
  • the temperature in the aforementioned step (c) is preferably at least 900 °C, more preferably at least 1000 °C.
  • the temperature in step (c) is 900 °C to 1200 °C, in particular 1000 °C to 1200 °C, particularly 1000 °C.
  • step (c) is carried out by applying a constant or variable DC voltage of 500 V at 1000 °C for 1 h to the samples obtained in step (b) or the shaped bodies, in particular discoidal shaped bodies, thereof.
  • step (d) may be carried out by cooling the samples obtained in step (c) to room temperature.
  • step (d) may be carried out for 1 min to 72 h, in particular 15 min to 5 h, preferably 15 min to 2 h.
  • the permanently polarized hydroxyapatite is obtained or obtainable by a process comprising the steps of
  • the contacting step is carried out in the presence of liquid water and/or water vapor.
  • the water is in liquid form and/or vapor form, for carrying out the contacting step.
  • the contacting step is carried out with a volumetric ratio of permanently polarized hydroxyapatite to water, in particular liquid water and/or water vapor, of 1000:1 to 0.01:1, in particular 500:1 to 100:1, preferably 300:1 to 350:1.
  • the contacting step is carried out with carbon dioxide alone.
  • the contacting step is carried out with a volumetric ratio of carbon dioxide to methane of 200:1, in particular 3:1, preferably 1:1.
  • the contacting step is carried out under a total pressure of 0.1 bar to 100 bar, in particular 0.1 bar to 10 bar, in particular 1 bar to 10 bar, in particular 1 bar to 8 bar, in particular 1 bar to 6 bar, preferably of 6 bar.
  • total pressure refers to the carbon dioxide pressure (when this gas is used alone) or to the sum of each gas partial pressure of the gas mixture, preferably at room temperature.
  • the contacting step is carried out under a pressure of carbon dioxide of 0.035 bar to 90 bar, in particular 0.1 bar to 10 bar, in particular 1 bar to 8 bar, preferably of 6 bar.
  • the contacting step is carried out under a partial pressure of carbon dioxide of 0.035 bar to 90 bar, in particular 0.1 bar to 3 bar, in particular 1 bar to 3 bar, preferably of 3 bar, and/or under a partial pressure of methane of 0.00017 bar to 5 bar, in particular 1 bar to 3 bar, preferably of 3 bar.
  • the contacting step may be carried out with a total pressure of the gas mixture from 0.0001 bar to 250 bar in the presence of the catalyst and the water, in particular liquid water.
  • the contacting step may be carried out with a pressure ratio of carbon dioxide to methane (CO 2 : CH 4 ) in the presence of the catalyst from 0.0001 bar : 250 bar to 250 bar : 0.0001 bar.
  • the gas mixture may be in particular free of nitrogen (N 2 ).
  • the contacting step may be carried out in the absence of nitrogen.
  • the contacting step is carried out with a molar ratio of carbon dioxide to permanently polarized hydroxyapatite of 0.1 to 0.5, in particular 0.2 to 0.5, preferably 0.3 to 0.5.
  • the contacting step is carried out with a molar ratio of methane to permanently polarized hydroxyapatite of 0.1 to 0.5, in particular 0.2 to 0.5, preferably 0.3 to 0.5.
  • the contacting step is carried out by using an uncoated permanently polarized hydroxyapatite, i.e. by using a permanently polarized hydroxyapatite lacking any coating.
  • an uncoated permanently polarized hydroxyapatite advantageously significantly increases the conversion of carbon dioxide into functionalized organic molecules having 2 and/or 3 carbon atoms (such as ethanol and/or acetic acid and/or acetone) and particularly in addition maximizes the selective synthesis of ethanol as the major reaction product.
  • the application of an uncoated permanently polarized hydroxyapatite advantageously significantly increases the conversion of carbon dioxide and methane into ethanol and particularly in addition maximizes the selective synthesis of ethanol as the major reaction product.
  • the contacting step may be carried out by using a coated permanently polarized hydroxyapatite.
  • the contacting step may be carried out by using a permanently polarized hydroxyapatite being coated with an inorganic photocatalyst such as TiO 2 , MgO 2 , MnO 2 or combinations thereof.
  • the contacting step may be carried out by using a permanently polarized hydroxyapatite having a three-layered coating, in particular wherein the three-layered coating may be composed of two layers of aminotris(methylenephosphonic acid) and a layer of zirconium oxychloride (ZrOCl 2 ) or zirconia ZrO2, wherein the layer of zirconium oxychloride is arranged or sandwiched between the two layers of aminotris(methylenephosphonic acid).
  • ZrOCl 2 zirconium oxychloride
  • ZrO2 zirconia ZrO2
  • the contacting step is carried out under UV (ultraviolet) irradiation or UV-Vis (ultraviolet-visible) irradiation.
  • the contacting step may be carried out under UV irradiation or UV-Vis irradiation having a wavelength from 200 nm to 850 nm, in particular 240 nm to 400 nm, preferably 250 nm to 260 nm, more preferably of 253.7 nm.
  • the contacting step may be in particular carried out under UV irradiation having a wavelength from 200 nm to 280 nm, in particular 240 nm to 270 nm, preferably 250 nm to 260 nm, more preferably of 253.7 nm.
  • the permanently polarized hydroxyapatite is directly exposed to or irradiated with the UV irradiation or UV-Vis irradiation.
  • the UV irradiation or UV-Vis irradiation are/is provided by a suitable UV source and/or Vis source, for example UV lamp and/or Vis lamp.
  • the contacting step is carried out under UV (ultraviolet) irradiation or UV-Vis (ultraviolet-visible) irradiation having a irradiance from 0.1 W/m 2 to 200 W/m 2 , in particular 1 W/m 2 to 50 W/m 2 , preferably 2 W/m 2 to 10 W/m 2 , more preferably of 3 W/m 2 .
  • UV ultraviolet
  • UV-Vis ultraviolet-visible
  • the contacting step is carried out at a temperature of 25 °C to 250 °C, in particular 95 °C to 140 °C, preferably of 95 °C.
  • the contacting step is carried out at a temperature of 95 °C and under UV irradiation.
  • These reaction conditions are especially useful for synthesizing, in particular selectively synthesizing, functionalized organic molecules having 2 carbon atoms (such as ethanol and/or acetic acid) in high yields.
  • the contacting step may be preferably carried out without UV irradiation and at a temperature of 25 °C to 250 °C, in particular 95 °C to 140 °C, preferably of 140 °C.
  • the reaction conditions according this embodiment result in the synthesis, in particular selective synthesis, of functionalized organic molecules having 2 carbon atoms (such as ethanol and/or acetic acid) in high yields.
  • the contacting step may be carried out for 0.0001 h to 120 h, in particular 24 h to 72 h, preferably 48 h to 72 h.
  • the process in particular the contacting step, may be carried out continuously or discontinuously, in particular as a batch process.
  • the contacting step may be carried out by using air, in particular traffic contaminated air, as gas mixture.
  • air in particular traffic contaminated air
  • functionalized organic molecules having 1 to 3 carbon atoms, in particular ethanol and/or acetic acid and/or methanol and/or formic acid and/or acetone, as valuable compounds and concurrently to remove carbon dioxide from air, in particular traffic contaminated air.
  • the process comprises a further step
  • the above further step is preferably carried out by dissolving and extracting the catalyst and/or by extracting a supernatant formed during or in the contacting step.
  • the process is used for producing or synthesizing, in particular selectively producing or synthesizing, ethanol.
  • the process is used for producing or synthesizing a mixture comprising or consisting of ethanol and at last one further functionalized organic molecule, preferably selected from the group consisting of methanol, formic acid, acetic acid, malonic acid and acetone.
  • the process is used for producing or synthesizing a mixture comprising or consisting of ethanol and at last one further functionalized organic molecule selected from the group consisting of methanol, formic acid, acetic acid and acetone.
  • the process is preferably used for producing or synthesizing a mixture comprising or consisting of ethanol and at last one further functionalized organic molecule selected from the group consisting of methanol, acetic acid, malonic acid and acetone.
  • the process is used for producing or synthesizing a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone.
  • the process is used for producing or synthesizing a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone.
  • the present invention relates to the use of the process according to the present invention for removing carbon dioxide from an atmosphere, in particular from air, i.e. atmosphere of Earth.
  • the present invention relates to the use of the process according to the present invention for removing carbon dioxide from polluted or contaminated air such as traffic contaminated air.
  • air or "atmosphere of Earth” as used according to the present invention means a layer of gases retained by Earth's gravity, surrounding the planet's Earth and forming its planetary atmosphere.
  • the present invention relates to the use of a process comprising the step of
  • said use of the process is for the production or synthesis, in particular selective production or synthesis, of ethanol or a mixture comprising or consisting of ethanol and at least one further functionalized organic molecule selected from the group consisting of methanol, formic acid, acetic acid, malonic acid and acetone, in particular to a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone, in particular with ethanol as a major reaction product, or to a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone, in particular with ethanol as a major reaction product.
  • Calcium nitrate (Ca(NO 3 ) 2 ), diammonium hydrogen phosphate ((NH 4 )2HPO 4 ; purity > 99.0 %) and ammonium hydroxide solution 30 % (NH 4 OH; purity: 28-30% w/w) were purchased from Sigma Aldrich. Ethanol (purity > 99.5 %) was purchased from Scharlab. All experiments were performed with milli-Q water.
  • the precipitates were separated by centrifugation and washed with water and a 60/40 v/v mixture of ethanol-water (twice). After freeze-drying it for three days, the white powder obtained was sintered for 2 h at 1000 °C in air using the Carbolite ELF11/6W/301 furnace.
  • TSP Thermally stimulated polarization process
  • Vibrational spectra for a structural fingerprint were obtained by the inVia Qontor confocal Raman microscope (Renishaw), equipped with a Renishaw Centrus 2957T2 detector and a 785 nm laser.
  • the 2 x 1 x 2 HAp supercell was chosen to build the (0001) facet for p-HAp.
  • the latter was built by removing an OH - orthonormal to the surface from the HAp supercell, which was previously optimized at the chosen DFT level. Consequently, a +1 global charge was applied for all calculations except for those involving formate, unpaired spin being considered when necessary.
  • the initial coordinates of HAp were optimized following the computational details provided below to unwind surface tensions.
  • the plane waves approach implemented in the Quantum Espresso 4.6 suite of Open-Source computer codes was used. Calculations were performed at the PBE level of theory corrected with the Grimme three body dispersion potentials (PBE-D3), applying the default C 6 software coefficients.
  • a kinetic energy cutoff for the wave functions of 40 Ry was employed.
  • a k-point mesh of 3 x 3 x 1 was automatically generated. Instead, a Gamma-center 1 x 1 x 1 k-mesh was used for calculations of discrete molecules and a 7 x 7 x 7 k-mesh for the bulk HAp calculations.
  • Geometry optimizations were performed using the conjugated gradient algorithm until both the energy and force variation between consecutive steps was below 10 -3 a.u and 10 -4 a.u, respectively. The energy at each step was optimized until the deviation from self-consistency was below 10 -5 Ry.
  • Adsorption energies were calculated according to the following process: A+S ⁇ AS*, where A is the adsorbate; S the surface and AS* the adsorbed state.
  • a high pressure stainless steel reactor which was designed ad hoc, was used to perform all the reactions.
  • the reactor was dotted with a manometer, an electric heater with a thermocouple and an external temperature controller.
  • the reactor was also characterized by an inert reaction chamber coated with a perfluorinated polymer (Teflon, 120 mL), where both the catalyst and water were incorporated.
  • the reactor was equipped with three independent inlet valves for the incorporation of gases and an outlet valve to recover the gaseous reaction products.
  • a UV lamp (GPH265T5L/4, 253.7 nm) was also placed in the middle of the reactor to irradiate the catalyst directly, the lamp being protected by a UV transparent quartz tube. All surfaces were coated with a thin film of perfluorinated polymer (Teflon) in order to avoid any contact between the reaction medium and the reactor surfaces, in this way discarding other catalyst effects.
  • Three-layered systems consisting of the successive deposition of aminotris(methylenephosphonic acid) (ATMP) and zirconium oxychloride (ZC) onto p-HAp were obtained by immersion in the corresponding aqueous solutions at room temperature for 5 h.
  • ATMP aminotris(methylenephosphonic acid)
  • ZC zirconium oxychloride
  • p-HAp was immersed into a 5 mM ATMP solution for 5 h.
  • ZC was deposited onto the ATMP layered p-HAp by immersing the latter into a 5 mM ZrOCl 2 solution for 5 h.
  • a second layer of ATMP was deposited on the ZC and ATMP layered p-HAp by immersing the latter into a 1.25 mM ATMP solution for 5 h.
  • Functionalized organic molecules having 1 to 3 carbon atoms were synthesized from CO 2 gas alone (1, 2, 4 or 6 bars) as well as from CO 2 and CH 4 gas mixture (3 bar each) in the presence of uncoated p-HAp as catalyst and in the presence of liquid H 2 O (1 mL).
  • the reaction was carried out for 24, 48 or 72 h at 95, 120 or 140 °C and under irradiation of an UV lamp (GPH265T5L/4, 253.7 nm) illuminating directly the uncoated p-HAp or without UV radiation.
  • Functionalized organic molecules having 1 to 3 carbon atoms were synthesized from CO 2 and CH 4 gas mixture (3 bar each) in the presence of coated p-HAp as catalyst and in the presence of liquid H 2 O (1 mL). The reaction was carried out for 72 h at 95 °C and under irradiation of an UV lamp (GPH265T5L/4, 253.7 nm) illuminating directly the coated p-HAp.
  • the p-HA was coated with two layers of aminotris(methylenephosphonic acid) and a layer of zirconium oxychloride (ZrOCl 2 ), wherein the layer of zirconium oxychloride was arranged or sandwiched between the two layers of aminotris(methylenephosphonic acid).
  • the yields (expressed as ⁇ mol of product per gram of coated p-HAp) obtained from the solution obtained after extraction by dissolving the catalyst were: ethanol (16.1 ⁇ 3.2 ⁇ mol/g), methanol (4.9 ⁇ 1.0 ⁇ mol/g), acetone (0.8 ⁇ 0.2 ⁇ mol/g) and acetic acid (0.6 ⁇ 0.1 ⁇ mol/g).
  • Ethanol was synthesized from CO 2 and CH 4 gas mixture (3 bar each) in the presence of coated p-HAp as catalyst and in the presence of liquid H 2 O (1 mL). The reaction was carried out for 72 h at 95 °C and under irradiation of an UV lamp (GPH265T5L/4, 253.7 nm) illuminating directly the coated p-HAp.
  • the p-HA was coated with two layers of aminotris(methylenephosphonic acid) and a layer of zirconium oxychloride (ZrOCl 2 ), wherein the layer of zirconium oxychloride was arranged or sandwiched between the two layers of aminotris(methylenephosphonic acid).
  • Ethanol was synthesized from CO 2 and CH 4 gas mixture (3 bar each) in the presence of (uncoated) HAp as catalyst and in the presence of liquid H 2 O (1 mL).
  • the reaction was carried out for 72 h at 95 °C and under irradiation of an UV lamp (GPH265T5L/4, 253.7 nm) illuminating directly the p-HAp.
  • the reaction resulted in a very poor yield of ethanol (1.9 ⁇ 0.5 ⁇ mol/g catalyst). Further, the yield of acetone and acetic acid was ⁇ 0.1 ⁇ mol/g catalyst.
  • Ethanol was synthesized from CO 2 and CH 4 gas mixture (3 bar each) in the presence of (uncoated) HAp as catalyst and in the presence of liquid H 2 O (1 mL). The reaction was carried out for 72 h at 95 °C and under irradiation of an UV lamp (GPH265T5L/4, 253.7 nm). In absence of any solid support acting as catalyst (see fig. 7(a) ), the yield of ethanol is practically 0 (0.1 ⁇ 0.05 ⁇ mol/g). Such a small amount, which has been attributed to eventual photo-induced CO 2 reduction and water splitting, completely disappears in absence of UV radiation (see 7(b)).
  • the formation of functionalized organic molecules having 1 to 3 carbon atoms might be associated to the pressure of the feeding gas, the temperature and the reaction time.
  • the process without UV illumination at was repeated using CO 2 gas and uncoated p-HAp as catalyst.
  • the yield of functionalized organic molecules having 1 to 3 carbon atoms increases with pressure.
  • the total yield (sum of the yields obtained for each product by dissolving the catalyst + sum of the yields obtained for each product from the supernatant) increased from 11.9 ⁇ 1.6 to 23.1 ⁇ 2.3 ⁇ mol/g when the pressure increases from 1 to 6 bars.

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EP20382918.9A EP3988523B1 (fr) 2020-10-21 2020-10-21 Procédé de production de molécules organiques fonctionnalisées
ES20382918T ES2942302T3 (es) 2020-10-21 2020-10-21 Proceso para producir moléculas orgánicas funcionalizadas
EP21720783.6A EP3953021B1 (fr) 2020-04-28 2021-04-27 Procédé de production de molécules organiques fonctionnalisées et leurs utilisations
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BR112022021718A BR112022021718A2 (pt) 2020-04-28 2021-04-27 Processo para produzir moléculas orgânicas funcionalizadas e usos das mesmas
CN202180046076.6A CN115956000A (zh) 2020-04-28 2021-04-27 用于产生官能化有机分子的方法及其用途
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JP2022565842A JP2023524232A (ja) 2020-04-28 2021-04-27 官能化有機分子を生成するための方法およびその使用
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KR1020227041561A KR20230005915A (ko) 2020-04-28 2021-04-27 관능화된 유기 분자의 제조 방법 및 이의 용도
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US17/921,755 US20230159417A1 (en) 2020-04-28 2021-04-27 Process for producing functionalized organic molecules and uses thereof
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